WO1997023424A1

WO1997023424A1 - Glass article covered with ultraviolet-absorbing colored coat

Info

Publication number: WO1997023424A1
Application number: PCT/JP1996/003759
Authority: WO
Inventors: Mitsuhiro Kawazu; Taro Miyauchi; Koichi Maeda; Tatsuya Noguchi
Original assignee: Nippon Sheet Glass Co., Ltd.
Priority date: 1995-12-26
Filing date: 1996-12-24
Publication date: 1997-07-03
Also published as: ES2164934T3; DE69615827T2; AU692121B2; US5876854A; EP0811583A4; AU1173097A; PT811583E; EP0811583B1; DE69615827D1; EP0811583A1

Abstract

A glass article wherein the surface of the glass as the base is covered with an ultraviolet-absorbing colored coat mainly comprising 5 to 50 % by weight of silicon oxide, 5 to 70 % by weight of titanium oxide, 20 to 80 % by weight of cerium oxide, 5 to 30 % by weight of at least one particulate colorant selected from the group consisting of gold, silver, platinum, palladium, cadmium sulfide and cadmium selenide, and 0 to 30 % by weight of at least one coloring metal oxide selected from the group consisting of cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, and iron oxide. The glass article can be controlled at will in color tone and transmittances of ultraviolet and visible rays.

Description

TECHNICAL FIELD The present invention relates to a glass article coated with an ultraviolet-absorbing colored film, particularly a glass article coated with an ultraviolet-absorbing colored film used for vehicles such as automobiles and windows of buildings. It relates to a glass plate. Background art

As a method for obtaining colored glass, (1) by applying silver or copper as an inorganic salt to the glass surface and then baking, the ultra-fine particles of silver or copper as an inorganic salt penetrate into the glass substrate and form a transparent colloidal color. There are ion exchange methods, or (2) a method in which gold ions are mixed with a metal alkoxide solution, applied to a substrate, and then heat-treated to precipitate gold fine particles. Other methods include (3) producing a metal film deposited on a glass substrate using a sputtering method.

On the other hand, as a method of forming an ultraviolet absorbing film on a glass substrate, a metal oxide such as zinc oxide, titanium oxide, or cerium oxide, which is an ultraviolet absorbing component, is coated on a glass substrate using a sol-gel method or a sputtering method. There is a method of forming an absorption film. For example, C 60 ₂ in a weight ratio: Ding 1 0 _2: 8 1 0 ₂ 64: 1 8:] ultraviolet absorbing film you containing 8 ratio, a method of forming on a glass substrate by a sol-gel method, It is described in Japanese Patent Application Laid-Open No. 6-192598.

The film on the glass substrate formed by the above-mentioned various methods is colored but does not have ultraviolet absorbing performance, or has ultraviolet absorbing performance but is not colored. Further, in Japanese Laid-6-1 9 1 896 JP-colored film containing silicon oxide, titanium oxide and gold microparticles, for example, as a preferred composition, T i 0 ₂ 8 5~ 3 wt%, S i 0 4 0 Glass articles coated with a colored film in the range of 00% by weight and 185 1160% by weight are described. However, this colored film-coated glass article, T i 0 ₂ content When the amount is not much not sufficient ultraviolet shielding performance and T i 0 if many ₂ content higher ultraviolet blocking performance is obtained, but colored in blue to pink, that transparently light color and UV transmittance In addition, the visible light transmittance cannot be freely controlled. Disclosure of the invention

An object of the present invention is to provide a glass article coated with an ultraviolet absorbing colored film, which can freely control the color tone, ultraviolet transmittance and visible light transmittance. The present inventors have newly developed a glass article coated with an ultraviolet-absorbing colored film having a coloring function and a high ultraviolet ray blocking rate and capable of freely controlling the visible light transmittance in order to solve the above problems.

That is, the present invention, expressed in wt%,

Silicon oxide 5 to 50,

Titanium oxide 5 ~ 70,

Cerium oxide 20-80,

At least one fine particle for coloring selected from the group consisting of gold, silver, platinum, palladium, sulfurizing dome, and cadmium selenide

5-30,

At least one coloring metal oxide selected from the group consisting of cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, and iron oxide

0-3 0.

Is a glass article coated with a UV-absorbing colored film in which a UV-absorbing colored film containing as a main component is coated on a glass substrate. Each component of the composition of the ultraviolet absorbing colored film in the present invention will be described below.

Silicon oxide is necessary to maintain the strength of the film. If its content is too low, the strength of the film will be low and the visible light reflectance will be too high. Conversely, if the amount is too large, the transparency of the film decreases, and the ultraviolet absorbing performance also decreases. Therefore, the inclusion of silicon oxide The content is 5 to 50% by weight, preferably 30 to 50% by weight, and more preferably 15 to 40% by weight in terms of Si0.

Titanium oxide is necessary for forming a film containing silicon oxide and cerium oxide. If the content is too low, the film forming property and transparency of the film are reduced, and the ultraviolet absorbing ability is also reduced. I do. Conversely, if it is too large, the film-forming property is reduced and the visible light reflectance is too high. Accordingly, the content ^ the titanium oxide is 5-7 0% by weight in terms of T i 0 _2, preferably 5 to 4 5% by weight, more preferably 1 5-4 5 wt%.

Cerium oxide is a component necessary for absorbing ultraviolet rays, and if its content is too low, the ultraviolet absorbing ability is reduced and the film forming property is reduced. Conversely, if the amount is too large, the transparency of the film decreases. Therefore, the content of cerium oxide is 20 to 80% by weight, preferably 20 to 60% by weight, and more preferably 30 to 60% by weight in terms of Ce () _2. .

At least one type of coloring fine particles selected from the group consisting of gold, silver, platinum, palladium, sulfide dome and selenide dominate is necessary for obtaining a bright color, and its content is very low. If it is too high, sufficient coloring cannot be obtained, and if it is too high, the durability of the film decreases. Therefore, the content of the coloring fine particles (the total amount when a plurality of types are used in combination) is 5 to 30% by weight, preferably 10 to 20% by weight. Of these coloring fine particles, gold fine particles and a mixture of gold fine particles and palladium fine particles are preferably used because they are chemically stable, easily available, and inexpensive.

At least one coloring metal oxide selected from the group consisting of cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, and iron oxide shows a dark color by itself, but coexists with the above coloring fine particles. The color tone can be adjusted to show a preferable color tone, and the visible light transmittance can be arbitrarily adjusted in the range of 20% to 80 _(If the content is too large, the visible light reflectance of the film is reduced. Therefore, the content of the metal oxide for coloring (when a plurality of types are used in combination) is Co 0 and C r, respectively. O, C u 0, 1 ^ 1 ₁ 1 0, 1 ^ 1 0, in terms of Oyobi 1 ^ 6 ₂ 0 0-3 0% by weight, preferably Ku is 0-1 8.0 wt%, more preferably from 2 to 1 0. 0% 0. _(thickness of the ultraviolet absorbing colored film is lower is too much small ultraviolet absorptivity, Mr. Su Therefore, the thickness is preferably 30 to 200 nm, and more preferably 45 to 150 nm. The UV-absorbing colored film has a refractive index of 6.3-3.20 so that the glass plate having the UV-absorbing colored film is on an automobile window, and the coating surface of the glass plate is on the inside of the vehicle. If installed, the visible light reflectance from the inside of the vehicle is too high, which may obstruct the driver's view. The ratio is preferably as small as possible, about 20% or less, 10% or less, and 8% or less. Further, if the visible light reflectance of the glass plate viewed from the outside of the vehicle is too high, the glass plate has a glaring appearance, so that the visible light when the light is incident from the surface opposite to the coated surface of the glass plate is preferable. The reflectivity is preferably as small as possible at about 20% or less, more preferably at most 10%, and more preferably at most 8%. The value (saturation) of (a ² + b ² ) ^1/2 calculated from the values of a and b in the color system is preferably 10 or less, more preferably 5.0 or less, and still more preferably 2. is 0 or less in. the present invention, during the UV absorbing colored film and the glass article substrate, an intermediate layer containing silicon oxide, i.e., silicon oxide, in terms of S i 0 _2, 2 0 To 100% by weight, preferably 30 to 90% by weight, titanium oxide, dioxide Koniumu oxide parsley © beam, at least one gold厲酸product selected from the group consisting of zinc oxide and evening tantalum (the total amount when used in combination of plural kinds are), respectively T i 0 _2, Z r 0 in terms of _2, C e 0 _2, Z n 0 and T a ₂ 0 _5, 0 to 7 0 weight 9, more preferably 2 0-6 5 wt%, gold, silver, platinum, palladium, sulfide force 0 to 30% by weight, more preferably 5 to 20% by weight, of at least one kind of coloring fine particles selected from the group consisting of a domeme and a selenized cadmium (when a plurality of kinds are used in combination). % Of the intermediate layer having a refractive index lower than the refractive index of the ultraviolet absorbing film.

The intermediate layer has a refractive index of 1.45 to 2.05 and is at least 0.] 0, more preferably at least 0.2 lower than the refractive index of the ultraviolet absorbing film. It is adjusted by adding titanium oxide and other metal oxides and coloring fine particles as needed. By adjusting the refractive index and the film thickness of the intermediate layer having a low refractive index, the reflectance of visible light can be reduced, and the reflection color tone is adjusted to a color preferably close to neutral gray. be able to. The intermediate layer preferably has an intermediate refractive index between the refractive index of the ultraviolet absorbing film and the refractive index of the base glass (usually 1.51 to 1.52 for soda-lime silicate glass). In order to reduce the reflectance of visible light and enhance the reflection of near-infrared light, the refractive index of the ultraviolet absorbing film is η, and the refractive index of the intermediate layer and the film thickness (nm) are n ₂ and t, respectively. If the refractive index of the base glass is η ₃ and λ is a light wavelength (nm) in the range of 400 to 700 nm, then n satisfying the following equations (1) and (2): It is preferred to choose ₂ and t.

(η + (η) / 4 ≥ (η) ¹ /2-(η _Ι -η ₃ ) / 4 (1) t 2; 1 / 4π ₂ (2) Instead of providing the above-mentioned intermediate layer containing silicon oxide By providing a layer having the same composition as that of the intermediate layer (referred to as a low refractive index uppermost layer) on the ultraviolet absorbing colored film, the reflectance of visible light can be reduced, and the reflection color tone is preferably neutral. It can be adjusted to a color close to gray.

The refractive index of the lower refractive index uppermost layer is such that the reflection color of the ultraviolet absorbing glass is made neutral and the reflection light at the interface between air and the lower refractive index uppermost layer is reduced in order to reduce the visible light reflectance. It is preferable to satisfy the condition that the reflected light at the interface between the uppermost layer and the ultraviolet absorbing film is canceled.

That is, assuming that the refractive index of the low refractive index uppermost layer is η ₄ , the refractive index of the ultraviolet absorbing film is η, and the refractive index of air is η ₃ , the perfect non-reflection condition for the refractive index is η 4 = (η, η ₃ ) ' ^{/ 2} and η 1, the perfect non-reflection condition is η ₄ = η, ^1/2 . Refractive index eta ₂ is antireflection effect be outside slightly from the equation of the low refractive Oriritsu uppermost layer is large, therefore, eta ₄ 9 0-1 1 0% of the square root of the refractive index of the ultraviolet absorbing film, i.e.,

1.10 X η ι ^1/2 ≥ η ₄ ≥ 0.90 x η It is preferable to satisfy the expression (3) of (3), more preferably 95 to! It is preferably 05%. The refractive index of the ultraviolet absorbing film is preferably 1.8 or more in order to obtain a non-reflection condition with the low refractive index uppermost layer.

Another condition is that the thickness t after firing of the low refractive index uppermost layer is an optical film thickness of a wavelength of 400 to 700 nm; Actually, it is preferable that the thickness is in the range of + 10% to 110% with respect to the thickness thereof.

1. lx A / (4 n ₄ ) ≥ t ≥ 0.9 X λ, / (4 n) (4). More preferably, the film thickness may be 0.95 to 1.05 times the 1/4 wavelength of visible light of 500 to 600 ηm.

The coloring fine particles show different coloring depending on the value of the refractive index of the matrix, and when the matrix has a high refractive index, it is colored near blue, and when the matrix has a low refractive index. Color to a color close to pink. When the intermediate layer or the lower refractive index uppermost layer also contains coloring fine particles, particularly fine particles of the same type as the coloring fine particles in the ultraviolet absorbing film, the coloring fine particles in the intermediate layer (or the lower refractive index uppermost layer) , Middle layer

(Or the uppermost layer having a low refractive index) has a different coloration from the coloring fine particles in the ultraviolet absorbing film having a different refractive index, so that the film as a whole exhibits a composite transmitted light tone. As described above, when the glass plate having the two-layer structure is mounted on an automobile window, the reflectance of visible light from the coated surface side of the glass plate and from the glass surface is as low as about 20% or less. Smaller is preferable, and opposite to the coated surface of the glass plate The reflection tone from the side (glass side) is also preferably close to neutral gray, and is calculated from the values of a and b in the Lab color system (a ² + b ² ) ^{1 2} (saturation) Is preferably 10 or less, more preferably 5.0 or less, and even more preferably 2.0 or less.

The glass article coated with an ultraviolet-absorbing colored film of the present invention has a point a ′ (a = 0, b = 0), a point A ′ (a = 25, b = 0), a point B ′ ( a = 0, b = — 2 5), point C '(a = 0, b = 2 5), and point 0' in that order, point 0 'and point A', and point C 'and point 0' Each of the straight lines preferably has a color tone in a sector 內 formed by connecting points A ′ and B ′ and points B ′ and C ′ with arcs of a circle centered on point 0 ′, respectively. More preferably, expressed in the Lab color system, point 0 (a = 0, b = 0), point A (a = 20, b = 6), point B (a = 0, b =-20. 9), point C (a = -6, b = 20) and point O in that order, point 0 and point A, and point C and point 0 as straight lines, respectively, point A and point B, and point B And the point C are connected by arcs of a circle centered on the point 0, respectively, and have a color tone of the transmitted light within a sector formed by the circle. Further, by using a 1.5-5.5 mm thick transparent glass substrate colored green as the glass substrate in the present invention, an ultraviolet shielding glass plate having a transmission color close to neutral gray can be obtained. can get. The color tone of the transmitted light due to the coloring particles in the ultraviolet absorbing colored film changes depending on the refractive index of the matrix of the film. The refractive index of this film should be 1.65 to 1.76, and the film composition should be

Silicon oxide 30-50,

Titanium oxide 5 ~ 4 5,

Cerium oxide 20-60,

However, the sum of titanium oxide and cell oxide is 35-55,

Fine particles for gold coloring 5 ~ 30,

Is selected as a main component, and the green color glass substrate, particularly the transmitted light, has an a value of 1 10.0 to -4.0 in the Lab color system, and -1.0 to 4.0 b By combining with a glass plate having a chromaticity of, the transmitted color close to neutral gray, in particular, the transmitted light is represented by the Lab color system, where a is −5. () To 5.0 and b is − A colored coated glass plate having a color tone in the range of 5.0 to 5.0 and a transmission color represented by a lightness in which L is 60 to 90 is obtained.

The UV-absorbing colored film itself having a refractive index of 1.65 to 1.76 shows reddish purple to purple coloring, but this color is combined with the green color of the glass substrate that has a complementary color relationship, resulting in neutral gray If the refractive index of the ultraviolet absorbing colored film is higher than 1.76, the color of the film itself becomes blue, and in combination with the green glass substrate described above. However, a color close to neutral gray cannot be obtained, and it becomes more turquoise. In the above, the case where the coloring particles are contained in the ultraviolet-absorbing colored film has been described. However, an intermediate layer having a low refractive index is provided between the ultraviolet-absorbing colored film and the glass article substrate, or the same composition as the intermediate layer is used. When the layer (hereinafter referred to as the “low-refractive-index top layer”) is provided on the above-mentioned ultraviolet-absorbing coloring film, instead of including the coloring fine particles in the ultraviolet-absorbing coloring film, the intermediate layer (or the low-refractive-index top layer) May be contained.

In other words, the second invention expresses, in terms of% by weight,

Silicon oxide 5 to 50,

Titanium oxide 5 ~ 70,

Cerium oxide 20-80,

An ultraviolet-absorbing colored film containing, as a main component, between the ultraviolet-absorbing colored film and the glass substrate or on or above the ultraviolet-absorbing film, expressed in terms of% by weight: gold, silver, platinum, c ° At least one kind of coloring fine particles selected from the group consisting of radium, sulfurizing dome, and cadmium selenide

5-30,

Silicon oxide 5 ~ 95,

At least one metal oxide selected from the group consisting of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide

(To use multiple items, add them up) 0 ~ 70, At least one metal oxide for coloring selected from the group consisting of cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide and iron oxide

(Total when multiple items are used) 0 ~ 30,

Containing, middle layer (or the low refractive index uppermost layer) _c the intermediate layer is a glass article coated with UV absorbing colored film was formed having a refractive index lower than the refractive index of the ultraviolet absorbing film (or As the low refractive index top layer, at least one selected from the group consisting of cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, and iron oxide, in addition to the colloidal fine particles for coloring and silicon oxide. The color tone of the transmitted light can be adjusted by further adding the metal oxide of the present invention, and the visible light transmittance can be arbitrarily adjusted in the range of 20% to 80%.

The coloring metal oxide is contained in the intermediate layer (or the low refractive index uppermost layer) in a range of 0 to 30% by weight, preferably 0 to 18.0% by weight, and more preferably 0.2 to 1% by weight. 0.0% by weight. If the content is less than 0.2% by weight, the effect of reducing the coloring and the visible light transmittance is not produced. On the other hand, if it exceeds 30% by weight, the visible light transmittance becomes less than 20%, and the color tone is hardly seen, which is inconvenient.

The intermediate layer (or the uppermost layer having a low refractive index) is at least one selected from the group consisting of the coloring fine particles, silicon oxide, cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, and iron oxide. By further containing at least one metal oxide selected from the group consisting of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide, in addition to one kind of coloring metal oxide, UV absorption performance can be enhanced and visible light transmittance can be arbitrarily adjusted within the range of 20 to 80%.

At least one metal oxide selected from the group consisting of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide, when contained in the intermediate layer in a plurality, is 0 to 7 in total. It is contained in the range of 0% by weight, preferably 5 to 70% by weight. If the content is less than 5% by weight, the effect of enhancing the ultraviolet absorbing performance is not produced. Conversely, if the content exceeds 70% by weight, the film strength is disadvantageously reduced. In the present invention, by changing the type and amount of the colored colloidal fine particles or changing the ratio of silicon oxide, titanium oxide, and cell oxide to change the refractive index of the film, various colors such as red, blue, and yellow can be obtained. A transparent color can be realized, and by containing at least one oxide selected from the group consisting of Co, Cr, Cu, Mn, Ni, and Fe, the visible light transmittance is 20%. It can be adjusted arbitrarily at about 80% .Furthermore, by adopting a two-layer structure using a low refractive index layer as an undercoat or the top layer, the reflectance can be lowered and the reflection color can be adjusted. can do. Among the fine particles for coloring used in the present invention, chloride or nitrate such as chloroauric acid, silver nitrate, or palladium chloride is suitable as a raw material for fine particles of silver, platinum, or palladium, but is stable and soluble. If there is, there is no particular limitation. Raw materials for the cadmium sulfide and cadmium selenide fine particles include acetic acid cadmium, nitric acid cadmium, cadmium chloride, and SeC (NH ₂ ). The ultraviolet absorbing colored film containing colored fine particles of the present invention comprises, on a substrate, a solution comprising a compound for forming colored fine particles, raw materials of silicon oxide, titanium oxide, and cerium oxide, and if necessary, a catalyst, an additive, and an organic solvent. It is obtained by drying after application and baking. Sulfurizing power The dough is obtained by performing a sulfurizing treatment in the above calcination process.

In addition, as a raw material of silicon oxide, titanium oxide, and cerium oxide for forming a colored film in the present invention, any material can be used as long as it can form a transparent film by a sol-gel method, and is specifically described below. As a raw material of silicon oxide, metal alkoxide is preferable, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Condensates (n≥2) or mixtures of these condensates are also conveniently used. For example, condensates include hexethoxydisiloxane (n = 2), octaethoxytrisiloxane (n = 3), decaethoxytetrasiloxane (n = 4), and ethoxypolysiloxane (n≥5). it can. single Silicate 40 composed of a mixture of a monomer (n = 1) and a condensate (n≥2) [Composition is described in J. Cih 1 ar, Colloids and Surfaces A: Physicochera. Eng.

Aspects 70 (1993), pp. 253 to 268, monomer (n = 1): 12.8% by weight, dimer (n = 2): 10.2 by weight fraction Wt%, trimer (n = 3)

: 12.0% by weight, tetramer (n = 4): 7.0% by weight, multimer (n≥5): 56.2% by weight, ethanol: 1.8% by weight] It can be suitably used. Further, an alkyl trialkoxysilane in which the alkoxy group of the above compound is substituted with an alkyl group can also be used. For example, when the alkoxy group is a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group or an octyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, Alkenyl groups such as vinyl group, aryl group, y-methacryloxypropyl group and _7- acryloxypropyl group, aralkyl groups such as phenyl group, tolyl group and xylyl group, and aralkyl groups such as benzyl and phenethyl group. Examples thereof include those substituted with a group or a mercaptopropyl group, an archloropropyl group, a ₇ -aminopropyl group, or the like. As a raw material of titanium oxide, an organic compound of titanium such as titanium alkoxide, titanium acetyl acetate, or titanium carboxylate is preferably used. The titanium alkoxide is generally represented by T i (OR) (R is an alkyl group having up to 4 carbon atoms), but titanium isopropoxide and titanium butoxide are preferable in view of reactivity. It has also been known that in the case of titanium, it is preferable to use acetyl acetate in view of its stability. In this case, the general formula is represented by T i (OR) mLn (m + n = 4, n ≠ 0), where L is acetylacetone. In this case, the titanium alkoxide may be converted to acetylacetonate with acetylacetone, or a commercially available titanium acetyl acetate may be used. Furthermore, it is conceivable to use a carboxylate. As a raw material for cerium oxide, organic compounds of cerium such as cerium alkoxide, cerium acetyl acetonate, and cerium carboxylate can be suitably used. In addition, cerium inorganic compounds such as nitrates, chlorides, and sulfates can be used, but cerium nitrates and cerium acetyl acetate are preferred from the viewpoint of stability and availability. When alkoxides are used as raw materials for silicon oxide, titanium oxide, and cell oxide, the hydrolysis catalysts include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, propionic acid, and p-toluenesulfonic acid Organic acids such as are used. As a raw material for oxides of Co, Cr, Cu, Mn, Ni, and Fe to be contained in the ultraviolet absorbing colored film in addition to the above-mentioned colored fine particles, silicon oxide, titanium oxide, and cell oxide. Preferred are inorganic compounds such as nitrates and chlorides, organic acids such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid and stearic acid, and organic amines modified with alkanolamines. The coating liquid for coating the ultraviolet absorbing colored film is obtained by dissolving each raw material in a solvent and mixing them at a predetermined ratio.

The organic solvent used in the present invention depends on the film forming method. For example, as the organic solvent for the gravure coating method, flexographic printing method, and roll coating method, a solvent having a low evaporation rate is preferable. The reason that a solvent with a low evaporation rate is preferable is that if a solvent with a high evaporation rate is used, the solvent will evaporate before sufficient leveling is performed. The evaporation rate of the solvent is generally evaluated by a relative evaporation rate index with that of butyl acetate being 100. Solvents with a value of 40 or less are classified as solvents with "extremely slow" evaporation rates, and such solvents are preferred as organic solvents for gravure coating, flexographic printing and roll coating. For example, sorbet mouth solvent (ethylene glycol monoethyl ether), butyl solvent mouth solvent (ethylene glycol monobutyl ether), cellosolve acetate (ethylene glycol monoethyl ether) Tert-acetate), carbitol (diethylene glycol monoethyl ether)-hexylene glycol, diethylene glycol, tripropylene glycol, diacetone alcohol, tetrahydrofurfuryl alcohol and the like. The solvent of the coating solution used in the present invention desirably contains at least one such solvent. However, in order to adjust the viscosity, surface tension, etc. of the coating solution, a plurality of the above solvents are used. You may use it. Solvents having a high evaporation rate and a relative evaporation rate exceeding 100, such as methanol (61 ()), ethanol (340), n-propanol (110), and isopropanol (300) ) May be added to the above-mentioned solvents having a relative evaporation rate index of 40 or less. The coating method used in the present invention is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, and a printing method. In particular, printing methods such as a gravure coating method, a flexographic printing method, a roll coating method, and a screen printing method are preferable because of high productivity and high use efficiency of the coating liquid composition. The coating liquid for an ultraviolet absorbing colored film is applied on a glass substrate by the above-mentioned coating method, and then, in an oxidizing atmosphere, provided that the coating liquid forms a film containing cadmium sulfide fine particles. In a sulfur atmosphere, heat treatment is performed at a temperature of 100 ° C. to 400 ° C. for 5 to 200 minutes to precipitate fine particles for coloring in the film. Further, by baking at a temperature of 500 to 700 or more for 10 seconds to 5 minutes, an ultraviolet absorbing colored film having a thickness of 60 to 200 nm is formed. In the case of two-layer coating, the first layer is applied and dried by heat, the second layer is applied again and dried by heat, and the same operation is repeated.

When applying the above coating liquid, drying it, applying the coating liquid for the second layer as necessary, applying the masking coating to the dried glass plate as necessary, and then performing the bending, Z, or heat strengthening steps. In this case, the above-mentioned film firing can be used also in this bending and / or heat strengthening step, and no special film firing is required. Of the raw materials of silicon oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide and tantalum oxide for the intermediate layer (or the lower refractive index uppermost layer), silicon oxide, titanium oxide and cell oxide are as described above. Since the raw materials for the ultraviolet absorbing colored film can be used, the raw materials for zirconium oxide, zinc oxide, and tantalum oxide are described below.

The raw materials of zirconium oxide include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetrisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetra n-butoxy zirconium, and tetra sec-butoxy. Zirconium and tetra-t-butoxyzirconium can be conveniently used. It is also possible to use zirconium halide alkoxides such as zirconium monochloride trialkoxide and zirconium dichloride dialkoxide in which the alkoxy group of the compound represented by the general formula (4) is replaced by a halogen group. . In addition, an alkoxyzirconium organic acid salt in which at least one of the above alkoxy groups of the zirconium alkoxide is replaced with an organic acid such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid, and stearic acid is used. It can also be used. As a raw material of the zinc oxide, those obtained by dispersing zinc oxide fine particles in an organic solvent, organic zinc such as zinc acetyl acetate or zinc ethylhexanoate, or organic zinc modified with alkanolamines are preferable. As a raw material for the oxidized phthalate, alkoxides and organic phthalates are preferred. At least one kind of these titanium, cerium, tantalum, zirconium, and silicon materials and their mixing ratios are compatible and stable with solvents, colored fine particles and transition metal compounds, and optically refractive index, color, reflection color The mechanical is abrasion resistant, chemical durability Is preferably determined in consideration of the following. As the glass substrate in the present invention, an unreinforced glass plate, a tempered glass plate, a laminated glass plate, a double-layer glass plate, or the like having an uncolored or colored transparent soda lime silicate glass composition is used. Preferably, it is a colored glass plate that blocks heat rays, and its transmitted light has an a value of 11.0 to -2.0 in Lab display and a color of b of 14.0 to 4.0. Degree, more preferably —10.0 to −4.0, a value of a and 1.0 to 4.0 b value, and is colored light green, The transmittance of UV light of wavelength is 10 ~ 70%, the transmittance of visible light is 40 ~ 85%, the transmittance of sunlight is 20 ~ 80%, and the thickness is 1.5 ~ 5. A 5 mm automotive window pane is preferably used. An example of a preferred composition of the glass plate is S i 0 ₂ 72.4, Λ

_{0.] 3, F e 2 0} 3 ( total iron) 0. 558, F e O 0. 1 3 5. C a 0 8. 77, M g 0 3. 84. N a 2 0 1 3. 8 each % By weight. As a glass substrate, the transmittance of ultraviolet light having a wavelength of 370 nm (T370 nm) is 10 to 70%, more preferably the transmittance of ultraviolet light (Tuv) by ISO 950; nm ~ 2 97.5 The value obtained by multiplying and multiplying the transmittance at 5 nm pitch interval at 5 nm by the determined weighting factor) is 15% or less and the visible light transmittance is 40 to 85. %, More preferably 70 to 85%, the solar transmittance (also referred to as solar transmittance) is 20 to 80%, more preferably 40 to 65%, and the thickness is 1.5 mm-5 .5 mm automotive glass sheets are preferably used. By coating on such a glass substrate, a colored glass having high ultraviolet absorbing ability can be obtained. _{C In the} present invention, color and visible light can be obtained by combining coloring with metal fine particles and ultraviolet shielding by an ultraviolet absorbent. It is possible to control the transmittance and the UV transmittance freely, the UV transmittance is less than 55%, and the transmittance of UV at 370 nm is less than 55%. Preferably, a UV-shielding colored glass having the UV transmittance of 45% or less, particularly the UV transmittance (Tuv) of 12% or less can be produced. Also double layer coating Thereby, it is possible to control the reflectance using interference due to the film configuration, and to realize fine color tone adjustment. As described above, according to the ultraviolet absorbing colored glass of the present invention, the visible light transmittance and the transmitted light can be changed by changing the concentrations of the colloid fine particles for coloring and other coloring raw materials and the concentrations of cerium oxide, titanium oxide and silicon oxide. The color tone, reflected light color tone, and UV cutoff rate can be adjusted arbitrarily. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph showing the color tone of transmitted light according to an example of the present invention and a comparative example.

FIG. 2 is a graph showing the performance of the example of the present invention and the comparative example. Embodiment

Next, the present invention will be described in more detail with reference to specific examples.

[Example 1]

3 mol of acetylaceton was added to 1 mol of cerium nitrate hexahydrate, and the mixture was heated to 90 ° C. with stirring and treated for 1 hour. This solution was used as a cerium nitrate stock solution. This is made in 2 3. 2 96 C e 0 ₂ solids.

To 1 mol of titanium isopropoxide being stirred, 2 mol of acetyl acetone was added dropwise using a dropping funnel. This solution was used as a titanium oxide stock solution. This becomes 1-6. 5% T i 0 ₂ solids.

To 50 g of ethyl silicate ("Echirun ligate 40" manufactured by Colcoat Co., Ltd.), 6 g of 0.1 N hydrochloric acid and 44 g of ethyl ethyl solvent were added, and the mixture was stirred at room temperature for 2 hours. This solution was used as a silicon oxide stock solution. This amounts to 20% at S i 0 solids. In addition, chloroauric acid tetrahydrate was dissolved in an ethyl sorb solution to a concentration of 15%. Take 1.11 g of the cerium nitrate stock solution, 0.732 g of the titanium oxide stock solution, 0.65 g of the silicon oxide stock solution, and 6.2 g of ethylethyl cellosolve. Add 2 g, and finally add a solution of chloroauric acid tetrahydrate in Echilse mouth solution. 33 g was added and mixed and stirred to prepare a coating solution 1. The above-prepared coating liquid was spin-coated on a non-colored transparent glass substrate at a rotation speed of 1000 rpm for 10 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. Further, baking was performed at 720 ° C. for 120 seconds to obtain a glass plate having a colored film. The characteristics of the colored film in terms of visible light transmittance, sunlight transmittance, color (transmitted light), and transmittance of ultraviolet light with a wavelength of 370 nm (hereinafter also referred to as 370 nm transmittance) are described. The results are shown in Tables 1-3. The obtained colored film showed good results in chemical resistance and Taber resistance. The neutral color tone of the reflection color ((a ² + b ²⁾ the value of saturation is Ru represented by ^{1 2} 1 0 or less) were obtained. The reflection characteristic is a value measured when light is incident from the surface side (glass surface side) opposite to the coating film of the glass substrate.

[Example 2]

Of the stock solutions prepared in Example 1, 1.12 g of a stock solution of cerium nitrate, 1.05 g of a stock solution of titanium oxide, 0.25 g of a stock solution of silicon oxide, and 6.2 g of an ethyl acetate solution were added thereto. 0 g was added, and finally 1.33 g of a solution of chloroauric acid tetrahydrate in ethyl chloride was added and mixed and stirred to prepare a coating solution.

Tables 1 to 3 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating solution prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a neutral reflection color was obtained <

[Example 3]

To ethyl chloride, 15 g of cobalt chloride was added 100 mL of ethyl acetate and dissolved to make 100 g. This results in a 15% cobalt chloride hexahydrate solution.

Of the stock solutions prepared in Example 1 as the coating solution, 0.68 g of the stock solution of cerium nitrate, 0.68 g of the stock solution of titanium oxide, 0.12 g of the stock solution of silicon oxide, and the above 15% cobalt chloride Take 2.0 g of the hexahydrate solution, add 5.19 g of ethyl sorbate, and finally add 1.33 g of chloroauric acid tetrahydrate solution of ethyl sorbate, and mix and stir. A coating solution 3 was prepared. Tables 1 to 3 show the properties of the glass plate obtained by applying, air-drying, and heat-treating the coating solution 3 prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and taber resistance. In addition, a reflection color with a neutral color tone was obtained.

[Example 4]

Ethylcet mouth solve was added to 15 g of chromium chloride hexahydrate, and the mixture was dissolved at 0 g. This results in a 15% chromium chloride hexahydrate solution.

Among the stock solutions prepared in Example I as the coating solution, a stock solution of cerium nitrate was used.

Take 68 g, 0.68 g of the titanium oxide stock solution, 0.12 g of the silicon oxide stock solution, and 2. () g of the above 15% chromium chloride hexahydrate solution. Was added, and finally 1.33 g of a solution of chloroauric acid tetrahydrate in ethyl acetate was added and mixed and stirred to prepare a coating solution 4.

Tables 1 to 3 show the properties of the glass plate obtained by applying, air-drying, and heat-treating the coating solution 4 prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and taber resistance. In addition, a reflection color with a neutral color tone was obtained.

[Example 5]

As the first-layer coating solution, of the stock solution of Example 1, 2.5 g of the stock solution for silylation and 5.50 g of Solvent-Elusolve were added, and finally, 3-aminopropyltriethoxysilane was chlorided. 2.0 g of a 10% by weight ethyl chloride sorb solution of chloroauric acid tetrahydrate, which was equimolar to gold acid, was added and mixed and stirred to prepare a coating solution 5. The coating solution 6 used in Example] was used as the coating solution for the layer.

The above-prepared coating liquid 5 was spin-coated on an uncolored transparent glass substrate at 100 rpm for 10 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to produce an interlayer film. Next, a coating solution 6 was similarly formed on the intermediate film. further

Baking was performed at 720 ° C. for 120 seconds to obtain a glass substrate having a colored film. Characteristics of colored film Are shown in Tables 1-3. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a reflection color having a neutral color tone was obtained.

[Example 6]

To 388.68 g of tetrabutoxyzirconium, 260.28 g of ethyl acetylacetyl acetate was added and stirred for 2 hours. This solution was used as a zirconium stock solution. This is 1-7. 8% Z r 0 ₂ solids.

As the first-layer coating solution, 1.5% of the stock solution of Example 1 was used.

Add 2 g and 7.38 g of ethyl acetate solvent, and finally add the above zirconium stock solution to 1.

10 g was added and mixed and stirred to prepare a coating liquid 7. As the coating solution for the second layer, of the stock solutions prepared in Example II, 4 g of the stock solution of cerium nitrate, 1.13 g of the stock solution of titanium oxide, and 0.20 g of the stock solution of silicon oxide. 6.20 g of ethylcellosolve was added to the solution, and finally a solution of chloroauric acid tetrahydrate in ethyl ethyl acetate was added to the solution.

33 g was added and mixed and stirred to prepare a coating liquid 8.

In the same manner as in Example 5, except that the coating liquids 7 and 8 prepared above were used instead of the coating liquids 5 and 6 of Example 5, coating, air drying, and heat treatment of the glass plate obtained were performed. The characteristics are shown in Tables 1 to 3. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a reflection color having a neutral color tone was obtained.

[Example 7]

Coating solution 5 used in the first layer in Example 5 as the first layer coating solution, and cerium nitrate undiluted solution in the stock solution prepared in Example 1 as the second layer coating solution 1.14 g, 1.13 g of the titanium oxide stock solution, and 0.20 g of the silicon oxide stock solution, and 7.53 g of ethyl acetate solvent were added thereto, followed by mixing and stirring. 9 was produced.

Glass obtained by coating, air-drying, and heat-treating in the same manner as in Example 5 except that the above-mentioned coating liquids 5 and 9 were used instead of the coating liquids 5 and 6 in Example 5. Tables 1 to 3 show the properties of the plate. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a reflection color having a neutral color tone was obtained. [Example 8]

Instead of the coating liquids 5 and 6 of Example 5, coating liquid 7 used in Example 6 and coating liquid 3 used in Example 3 were used, respectively. Tables 1 to 3 show the characteristics of the glass plates obtained by air drying and heat treatment. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a neutral reflection color was obtained.

[Example 9]

Same as Example 5 except that the coating liquids 5 and 6 of Example 5 were replaced with the coating liquid 7 used in Example 6 and the coating liquid 4 used in Example 4. The properties of the glass plate obtained by coating, air drying and heat treatment are shown! 3 to 3. The obtained colored film showed good results in chemical resistance and Taber resistance. The thickness and the refractive index of this intermediate layer satisfied the above equations (1) and (2). The optical thickness was equal to 分の of the wavelength of light at a wavelength of 660 nm.

Was.

[Example 10]

Of the stock solutions prepared in Example 1 as the coating solution, 1.13 g of the stock solution of cerium nitrate, 1.13 g of the stock solution of titanium oxide, and 0.2 g of the stock solution of silicon oxide were added with ethyl acetate solution. 7.54 g was added and mixed and stirred to prepare a coating liquid 10. Instead of the coating liquids 5 and 6 of Example 5, the coating liquid 3 used in Example 3 and the above-mentioned coating liquid 10 were used, respectively, and coated, air-dried and heat-treated in the same manner as in Example 5. Tables 1 to 3 show the characteristics of the obtained glass sheets. The obtained colored film showed good results in chemical resistance and Taber resistance.

[Example 11]

Of the stock solutions prepared in Example 1 as the coating solution, take 1-79 g of a stock solution of cerium nitrate, 0.254 g of a stock solution of titanium oxide, and 0.21 g of a stock solution of silicon oxide. To the mixture was added 6.42 g of ethyl ethyl solvate, and finally, 1.33 g of a solution of chloroauric acid tetrahydrate in ethyl ethyl cellosolve was added and mixed with stirring to prepare a coating solution.

Tables 1 to 3 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating solution prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and fiber resistance.

[Example 12]

Take 1.378 g of a stock solution of cerium nitrate, 0.546 g of a stock solution of titanium oxide, 0.452 g of a stock solution of silicon oxide, and 6.2 g of an ethyl acetate solution. 9 g was added, and finally 1.33 g of a solution of chloroauric acid tetrahydrate in ethyl chloride was added and mixed and stirred to prepare a coating solution.

Tables 1 to 3 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating solution prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and Taber resistance. The _c the reflection color of the neutral tones are obtained

[Example 13]

Take 1.596 g of the cerium nitrate stock solution, 0.395 g of titanium oxide stock solution, and 0.327 g of silicon oxide stock solution, and prepare 6.3 g of ethyl chloride solution. 5 g was added, and finally 1.33 g of a solution of chloroauric acid tetrahydrate in ethyl chloride was added and mixed and stirred to prepare a coating solution.

Tables 1 to 3 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating solution prepared above in the same manner as in Example 1. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a neutral color reflection was obtained.

[Example 14]

As the glass substrate, the thickness 3. 4 mm green glass substrate (glass composition; S i 0 7 1. 0, AI 2 O 3 1. 53, F e 2 O 3 0. 52, C a O 8. 6 2 , M g 0 4. 0 6, N a 2 O 1 2. 3, K 2 0 0. 7 6, refractive index 1.5 1, luminous transparently rate Y a = 8 1. 2%, the solar radiation transmittance T g = 60.996, visible light reflectance R g = 7. 1%, UV transmittance (T370 nm) = 62.5%, UV transmittance (Tuv) 31.4%, transmission color tone: light green, and then transmitted light color expressed in chromaticity of ab color system degree _{a = - 4. 7, b =} 0. 9, transmitted light bright degree L = 9 1, the reflected light chromaticity a = - 1. 3, b = - 0. 2) using exactly the same coating as in example 2 Using this solution, this coating solution was spin-coated on the green glass substrate at 100 rpm for 10 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. After holding for 120 seconds in an electric furnace at 720 ° C, the glass was pulled up and press-formed, and immediately thereafter, it was air-cooled and tempered to obtain a bent glass sheet for automobiles. The bending shape was as designed, and no perspective distortion was observed. Tables 1 to 3 show the characteristics of the colored film. The obtained colored film showed good results in chemical resistance and Taber resistance.

[Example 15]

Except that the same green glass substrate used in Example 14 was used as the glass substrate, the same coating liquid as in Example 6 was used, and the coating, air drying, and heat treatment were performed in the same manner as in Example 6. Tables 1 to 3 show the properties of the obtained glass plate. The obtained colored film showed good results in chemical resistance and Taber resistance. Also, a reflection color with a neutral color tone was obtained.

(Table)) Example film Film composition (% by weight)

I 1U2 then eU2 AU then OU then ru f flit

1 UV absorbing film ί U. L 43 b lfa.u

2 Same as above U. / 46.4 16.0

07 0 00 c

ά b. 41.9 o (J.0

7 Q o 0

4 b.o ώ O .O 41.9 U.4

0 0

5 U. ί 43. D lb. U

5 Middle layer 84.0 16.0

6 UV absorbing film D. ϋ 30.7 46.4 16 0

H

b Intermediate layer 9-4 bu.b M nft Hft- UV absorbing film c> b.b 55.

7 Middle layer 84.0 16.0

6.3 27.8 41.9 23.5 0.5

o n

8 Middle layer 39.4 DU.b

9

6.3 7.8 41.9 23.5 0.4

r n

9 Medium H eyebrows oU.D c

10 UV absorbing film 8.2 36.6 55.2

10 Middle layer 6.3 27.8 41.9 23.5 0.5

11 UV absorbing film 7.9 7.9 68.2 16.0

12 Same as above 15.1 15.0 53.9 16.0

13 10.9 10.8 62.3 16.0

14 6.0 30. 7 46.4 16.0

15 6.0 30.7 46.4 16.0

15 Middle class 39.4 60.6 (Table 2) Example UV absorbing film Intermediate layer Thickness Refractive index Thickness Refractive index

(nm) (nm)

1 130 1.9

2 120 2.0

3 90 2.0

4 90 2.0

5 130 1.9 120 I.5

6 120 2.0 100 1.65

7 130 2.0 120 1.5

8 90 2.0 110 1.7

9 90 2.0 100 1.65

10 130 2.0 90 2.0

11 70 2.1

12 120 1.9

13 120 2.0

14 120 2.0

15 120 2.0 100 1.65

(Table 3) Implementation Y a T a Transmission color tone Transmission chromaticity Visible light Reflection chromaticity 370nm Example (%) (%) (a / b) Reflectance (a / b) Transmittance

(Force "lath surface") (%) (force "lath surface") (%)

1 55.2 63.8 Dark blue 0.37 /-10.13 12.07 3.98 / 7.13 45.2

2 68.0 65.5 Patina-895 / 2.85 13.22 3.35 / -3.95 45.6

3 65.9 66.4 Dark green 4 53 / -0.64 16.18 -0.50 / 1.18 47.5

59.5 66.4 -6.22 / -3.09 20.43 1.76 /-0.40 44.8 a 61.6 62.7 Magenta 15.08 / -6.27 lz.55 -2.61 / 3.56 41.2

6 68.0 65.5 Blue-green 9.55 / -3.30 13.22 3.62 / -4.16 43.1

7 63.3 68.7 Pink 9.52 / 4.85 13.55 -0.60 2.23 50.1

8 65.6 64.7 Light blue-green 9.65 / -1.29 14.24 7.29 / -2.86 46.7

9 72.6 74.8 Pale blue -6.72 / -0.22 6.67 10.72 /-3.09 44.7

10 62.7 63.7 Pale blue-6.26 / 4.93 13.49 -0.95 /-13.25 27.8

11 60.2 65.7 Patina -6.53 / 7.93 6.75 1.07 / 0.97 45.8

12 65.0 54.4 Patina \ .20 /-10.00 13.69 5.57 / 0.84 51.5

13 66.5 56.3 Patina -2.21 / -9.15 9.76 5.52 / 2.28 48.0

14 49.5 43.6 Blue-green -13.53 / -6.19 15.13 2.14 / -7.11 32.3

15 52.7 45.0 Positive green 12.42 / -5.58 10.83 0.56 / 2.15 33.8

[Comparative Example 1]

Take 1.11 g of the cerium nitrate stock solution prepared in Example 1, 0.732 g of the titanium oxide stock solution, and 0.605 g of the silicon oxide stock solution, and add the ethyl acetate solution to 7.55. g was added and mixed and stirred to prepare a tinting solution 11.

In the same manner as in Example 1, the coating liquid 11 prepared as described above was spin-coated on a non-colored transparent glass substrate at 1,000 rpm for 10 seconds. After air drying 2 50 at 2 Heat treatment was performed for a period of time to precipitate gold fine particles. Further, baking was performed at 720 for 120 seconds to obtain a glass substrate having a coloring film. Tables 4 and 5 show the properties of the colored film. The transmittance of the obtained colored film at 3700 nm was 63.6%, the ultraviolet absorbing ability was low, it was colorless and transparent, and no colored colored film was obtained.

[Comparative Example 2]

As a coating solution, 2.5 g of the stock solution of Example 1 and 6.17 g of a solvent solution of ethyl acetate were added, and finally, 3-aminopropyltriethoxysilane was added to the chloroauric acid. 2.0 g of a 10% by weight solution of chloroauric acid tetrahydrate in ethyl acetate was added and mixed and stirred to prepare a coating solution 12.

Tables 4 and 5 show the properties of the glass plates obtained by coating, air-drying, and heat-treating the coating solution 2 prepared above in the same manner as in Comparative Example. Although the obtained colored film was colored pink, the transmittance at 370 nm was 74.5%, and the ultraviolet absorbing ability was low.

[Comparative Example 3]

Of the stock solutions of Example 1, 1.07 g of the stock solution, 1.73 g of the titania stock, and 5.87 g of the ethyl acetate solvent were used as the coating solution. 1.33 g of ethyl sorbate solution of acid tetrahydrate was added, mixed and stirred to prepare a coating solution 13.

Tables 4 and 5 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating liquid 13 prepared above in the same manner as in Comparative Example 1. Although the obtained colored film was colored purple, it had a transmittance of 370 nm of 61.7% and a low ultraviolet absorbing ability.

[Comparative Example 4]

As a coating solution, 3.03 g of a titania stock solution and 5.64 g of an ethyl sorb solution were taken out of the stock solution of Example], and finally, a solution of chloroauric acid tetrahydrate in an ethyl solution of 1. 33 _{g was} added and mixed and stirred to prepare a coating solution 14.

Tables 4 and 5 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating liquid 14 prepared above in the same manner as in Comparative Example 1. The obtained colored film is colored blue. As a result, the transmittance at 370 nm was 5.5%, and the ultraviolet absorbing ability was high. Even when the amount of the titania stock solution in the coating solution 14 and the amount of the solution of chloroauric acid tetrahydrate in ethyl acetate solution were changed, the color tone did not change except for blue.

[Comparative Example 5]

Of the stock solutions of Example 1, 0.50 g of the stock solution of silica, 2.42 g of the stock solution of titania, and 5.75 g of the solvent solution of ethyl acetate were used as the coating solution. 1.33 g of a solution of ethyl ether in the mouth was added and mixed with stirring to prepare a coating solution 15.

Tables 4 to 5 show the properties of the glass plates obtained by applying, air-drying, and heat-treating the coating solution 15 prepared above in the same manner as in Comparative Example 1. The obtained colored film was colored blue, but had a transmittance of 370 nm of 58.6% and a low ultraviolet absorbing ability.

(Table 4) Comparative example Film composition (% by weight) Film thickness Refractive index

Si0 ₂ TiO _z Ce0 ₂ Au CoO CrO Zr0 ₂ (nm)

1 24.1 24.0 51.9 ―… 110 1.9

2 84.0 16.0 1 --- --- 180 1.5

3 36.1 47.9 16.0 --- ------- _{1 10} 1.8

4 84.0 16.0-100-2.2

5 16.8 67.2 16.0 ---- --- One 80 2.0

(Table 5) Ratio Y a T a Transmission color tone Transmission chromaticity Visible light Reflection chromaticity 370nra Comparison (%) (%) (a / b) Reflectivity (a / b) Transmittance Example (force lath surface) (% ) (Force lath surface) (%)

1 81.4 77.4 Colorless and transparent -0.55 / -1.34 19.5-1.81 / 3.71 63.6

2 73.6 78.1 Pink 10.30 / -4.33 6.7 3.62 /--0.96 74.5

3 67.0 66.3 Purple 2.88 /-14.69 11.3 4.69 / 5.09 61.7

4 54.8 57.7 Blue-15.88 / 11.07 13.7 3.19 / 6.12 51.5

5 50.2 61.7 -11.01 /-17.27 13.4 0.66 / 8.49 58.6

Next, the color tone of the transmitted light in the above Examples and Comparative Examples is shown in FIG. 2, and 3 and b are represented by points on rectangular coordinates in the 313 color system. Examples and comparative examples will be described.

When Examples 1, 2, 11, 11, 12, and 13 are compared with Comparative Examples 3, 4, and 5, a single-layer film containing Au fine particles and containing no cobalt oxide or the like (uncolored base material) Is However, there are the following differences.

(1) As shown in Fig. 2, the hue of the transmitted light (the positions of points where a and b are represented by rectangular coordinates in the Lab color system are polar coordinates, green is 180 degrees, blue is 270 degrees) Plotted on the abscissa and the transmittance of ultraviolet light (wavelength 370 nm) on the ordinate, the example has an ultraviolet transmittance of 55% or less and a transmitted light hue of 74 °. While a film that can be adjusted in a wide range can be obtained, in the comparative example, only a film that can adjust the transmitted light hue in a narrow range of about 15 degrees is obtained in a range having an ultraviolet transmittance of 55% or less. thing. (2) The transmitted light saturation (the value of (a ² + b ² ) ^{12 in the} Lab color system) obtained in the examples is ¹ for each of the examples 1, 2, 11, 1, 12, and 13. 0.1, 9.4, 10.3, 10.] and 9.4, which are relatively low values of 9 to 10 and are dark, whereas the comparative example is comparative example 3 , 4, and 5 are 15.0, 19.4, and 20.4, respectively, which are relatively high values of 15 to 20 and are bright colors. According to the glass coated with a single-layer film containing Au fine particles of the present invention, products having various hues as compared with the prior art can be obtained, and a product having a relatively low saturation can be obtained.

In Examples 3 and 4 in which a single-layer film (uncolored base material) further contains cobalt oxide or chromium oxide in addition to the Au fine particles, the transmitted light chroma was as low as 4.6 and 7.0, respectively. Darker colors with reflected light saturation of 1.3 and 1.8, and very neutral reflections with a saturation of 2 or less are obtained.

In Example 5 having an ultraviolet absorbing film containing Au fine particles and an intermediate layer containing silicon oxide and Au fine particles, compared to Example 1 having only an ultraviolet absorbing film of the same composition, The hue of the transmitted light changes greatly due to the combination of the coloring by the Au fine particles of Example 1 and the coloring by the Au fine particles in the intermediate layer. Is as high as 16

In Example 6 having an ultraviolet absorbing film containing Au fine particles and an intermediate layer containing silicon oxide and zirconium oxide, the reflection color tone was changed compared to Example 2 having only an ultraviolet absorbing film having the same composition. I have. Example 8 having an ultraviolet absorbing film containing Au fine particles and cobalt oxide and an intermediate layer containing silicon oxide and zirconia oxide, compared with Example 3 having only an ultraviolet absorbing film of the same composition, The hue of the transmitted light is almost the same (188 degrees in both Example 8 and Example 3), but the saturation is high (9.7 in Example 8 and 4.6 in Example 3). The light reflectance has decreased and the reflection color tone has also changed.

In Example 9 having an ultraviolet absorbing film containing Au fine particles and chromium oxide and an intermediate layer containing silicon oxide and zirconium oxide, the intermediate layer satisfies the non-reflection condition as described above. However, as compared with Example 4 having only the ultraviolet absorbing film of the same composition, the visible light reflectance is very small.

Example 10 having an ultraviolet absorbing film containing Au fine particles and another ultraviolet absorbing film containing silicon oxide, titanium oxide, and cerium oxide and not containing Au fine particles, It is effectively used when it is desired to increase the ultraviolet absorption capacity without changing the color tone of the contained ultraviolet absorbing film.

In Example 7 having an ultraviolet absorbing film containing no Au fine particles and an intermediate layer containing silicon oxide and Au fine particles, the transmitted light hue was a comparative example because the refractive index of the matrix of the Au fine particles in the intermediate layer was low. It is almost the same pink as 2, but has a higher ultraviolet absorbing ability than Comparative Example 2.

In Example 10 having an ultraviolet absorbing film containing no Au fine particles and an intermediate layer containing silicon oxide, cerium oxide, Au fine particles and cobalt oxide, Example 10 did not contain cerium oxide and cobalt oxide in the intermediate layer. Compared with Example 7, it has much higher UV absorption capacity.

In Example 14, which is a single-layer film containing Au fine particles and not containing cobalt oxide or the like (base material is green-colored glass), compared to Example 2 which differs only in that the base material is non-colored, Visible light transmittance is low, heat ray blocking performance and ultraviolet absorption performance are high, and the color tone of transmitted light and reflected light is changing.

Example 15 has an ultraviolet absorbing film containing Au fine particles, and an intermediate layer containing silicon oxide and zirconium oxide, and the substrate is a green colored glass. Compared with Example 6 which differs only in Example 6, the visible light transmittance is lower, the heat ray blocking performance and the ultraviolet absorbing power are higher, and the visible light hue is slightly changed.

[Examples 16 to 19]

As shown in Table 6 below, take the cerium nitrate stock solution, titanium oxide stock solution, and silicon oxide stock solution prepared in Example 1 respectively, add Ethylse mouth solve, and finally add chloroauric acid prepared in Example 1 A solution of tetrahydrate in ethyl acetate was added and mixed with stirring to prepare coating solutions 16, 18, and 19.

(Table 6) Coating liquid

1 6 18 1 9 Cerium nitrate stock solution 0.68 g 0.68 g 0.80 g

Titanium oxide stock solution 0.64g 0.64g 0.76g

Silicon oxide stock solution 1.19g 1.I9g 0.94g

Etinolace mouth sonolev 6.50g 6.16g 6.16g

Chloroauric acid tetrahydrate

Echilse π Solf "solution I. OOg 33g 1.33g

Green glass substrate of dimensions 1 Ocmx 1 Ocm each Koti ing solution prepared above to a thickness 3. 9 LRAM (I) (glass _{composition; S i 0 2 70. 4. A} 1 2 0 a 1. 5, Total iron _{_{(F e 2 0 3 0. 6}} 2, ( inner F e O 0.] _{8 5), C e 0 2} l. 67, T

1 0 ₂ 0 .1 4. C a 0 8.0, Mg O 4.0. N a ₂ 0 1 3. ϋ, Κ ₂ 0 0.70 wt%, refractive index 1.51, visual perception transmittance Y _a = 7 1. 6%, solar transparently ratio T g = 4 4. 7%, visible light reflectance R g = 6. 6%, transmission color; green, L ab color system chromaticity Express the transmitted light chromaticity a = -8.0, b = 3.4, reflected light chromaticity a = _1.9, b = -0.3) or the thickness of 3.5 and 1 Ocmx 10cm Green glass substrate (mouth) (The glass composition is the same as that of the above green glass substrate (a), luminous transmittance Ya = 73.5%, solar transmittance Tg = 48.5%, visible light Reflectance R g = 6.6%, transmitted color tone: 綠, expressed as chromaticity of Lab color system, transmitted light chromaticity a = -8.0, b = 3.4, reflected light chromaticity a = — 1. 9, b =-0.3, transmitted light dominant wavelength λ d = 52 2 nm, transmitted light stimulus purity P e = 2.29%, reflected chromaticity a = _ 1.9, b = — 0. 3) Spin coating was performed on the top for 100 rpm to 200 rpm at 10 rpm. After air drying, heat treatment was performed at 250 ° C for 2 hours to precipitate gold fine particles. And 7 more

Baking was performed at 20 ° C. for 120 seconds to obtain a glass plate having a colored film. The glass plates with a colored film produced using the coating liquid 16 are Examples 16 and 17, and the glass plates with a colored film produced using the coating liquids 18 and 19 are Example 1 respectively. 8 and 19. Tables 7 to 9 show the characteristics of the visible light transmittance, the sunlight transmittance, the color (transmitted light) of the colored film, and the transmittance of ultraviolet light having a wavelength of 370 nm. The obtained coloring film showed good results in chemical resistance and Taber resistance. The saturation of the transmitted color is 4.

3 to 7.8, and the saturation of the reflected color was (). 8 to 5.5. A reflected color with a low saturation and a color close to neutral gray was obtained. The reflection characteristic is a value measured by applying light from the glass surface side of the glass substrate.

(Table 7) Membrane Membrane composition (% by weight)

Example SiO _; TiO: CeO ₂ Au CoO CrO ZrO:

16 UV absorbing film 41.6 18.4 27.5 12.5

17 UV absorbing film 41.6 18.4 27.5 12.5

18 UV absorbing film 31.7 21.0 31.3 16.0

19 UV absorbing film 39.9 17.7 26.4 16.0

(Table 8) Glass UV absorbing film

Example Substrate (nm) Film thickness Refractive index

16 (a) 72 then 70

17 (a) 48 70

18 (Π) 68 then 76

19 (Π) 73 1.70

(Table 9) Actual Ya Tg Tuv T370 Transmitted chromaticity Visible light Reflected chromaticity

(%) (¾) (¾) (¾) (a / b) Reflectance (a / b)

Example (force lath) (%) (force lath)

16 55.9 40.0 6.3 18.0 -3.8 / -2.1 10.7 -1.2 / 2.7

17 58.9 41.3 6.3 18.2 4.9 / 0.2 10.0-0.4 / -0.7

18 46.6 36.6 5.7 -6.4 / -4.4 15.4 4.9 / 2.3

19 50.2 38.5 6.0 4.4 / -3.3 12.6 4.5 / 3.2

[Example 20]

Production of Pd raw material

2 mol of acetylacetone was added to 1 mol of palladium chloride, and the mixture was heated to 90 with stirring and treated for several hours. The precipitate was filtered, the solid content of the filtrate was measured, and after confirming the Pd content, it was used as a palladium stock solution.

Silicone stock solution 0.58, titanium oxide stock solution 0.93 g, cerium oxide stock solution 0.99 g, add ethyl sorbol 5.85 g, add 10 wt% chloroauric acid in ethyl chloride solution 1.5 g was taken, and finally 0.15 g of Pd stock solution was added to obtain a coating solution.

A green glass substrate having a thickness of 3.53 ram and a size of 1 Ocm × 10 era was coated on the substrate with the above prepared coating liquid (the glass composition was the same as that of the green glass substrate of Example 17; luminous transmittance Y a = 73.5%, solar transmittance T g = 48.5%, visible light reflectance R g = 7.0%, transmission color tone: green, transmission expressed in chromaticity of Lab color system Using light chromaticity a =-7.2, b = 3.0, reflected light chromaticity a =-2.4, b = _ 0.1.1), spin coating at 200 rpm / 10 seconds Went. After air drying, heat treatment was performed at 250 ° C for 2 hours to precipitate gold fine particles. Further, baking was performed at 720 times for 120 seconds to obtain a glass plate having a coloring film. Visible light transmittance (Y a) of glass plate with colored film Tables 10 and 2 show the optical properties such as sunlight transmittance (Tg), color (transmitted light), and transmittance of ultraviolet light (Tuv), and the film compositions. The obtained colored film showed good results in chemical resistance and Taber resistance. The reflection characteristic is a value measured by applying light from the coated surface side of the glass substrate.

(Table 10) Example Film composition (% by weight) Refractive index Film thickness

Sif Ti0 ₂ Ce0 ₂ Au Pd (nra)

2 0 20.0 26.5 39.6 12.5 87 50

(Table 11) Example Y a T g Tuv Transmission chromaticity lightness Glass surface

(%) (%) (%) (a / b / L) Visible light reflectance (%)

20 57.40.6 5.9 -6.2 / 3.8 / 76.1 13.2

(Table 12) Glass surface flk surface 1¾ surface

Example Reflected chromaticity Visible light reflectance Reflected chromaticity lightness

(a / b) (%) (a / b)

2 0-3.9 / 2. 17.3 0.4 / -3.7 [Example 2 ~ 5 1]

As glass substrates, two types of green glass substrates A and B having a size of 1 Ocm × 1 Ocm having a glass composition (% by weight), a plate thickness and optical characteristics shown in Table 13 are prepared.

(Table 13)

AB sio ₂ 71.0 70.4

1.53 1.5

(Of which FeO) 0.185

Ce0 ₂ 0 1.67

Ti0 ₂ 0 0.14

CaO 8.62 8.0

MgO 4.06 4.0

Na ₂ 0 12.3 13.0

20 0.76 0.70 Refractive index 1.51 1.51

Plate thickness (ram) 4.9 3.5

Ya (¾) 76.0 73.5

Tg (¾) 51.6 48.5

T370 (¾) 53.1

Tuv (%) 24.3 9.7

Visible light

Reflectance Rg (%) 6.9 6.6

Transmission color Green 綠 (Table 13) (continued)

Transparent I color a -6.5 8.0

Excessive degree b 0.5 3.4

Light I Dominant wavelength Ad (nm) 500 522

I Stimulation purity Pe (¾) 2.49 2.29

Reflected light chromaticity

a 1.7 -1.9

b -0.7 0.3

In order to obtain the film compositions shown in Tables 14 and 15 below, the cerium nitrate stock solution, titanium oxide stock solution, and silicon oxide stock solution prepared in Example 1, respectively, were taken and added to the ethyl acetate solution. Was added, and finally, a solution of chloroauric acid tetrahydrate prepared in Example 1 was added to the solution of ethyl acetate, and mixed and stirred to prepare six kinds of coating liquids. Tables 16 to 19 show the properties of the glass plates obtained by spin-coating at 100 to 200 rpm and coating, air-drying and heat-treating in the same manner as in Example 6. The obtained colored film showed good results in chemical resistance and Taber resistance. In addition, a reflection color having a neutral color tone was obtained.

(Table 14) Upper layer Lower layer Actual bending film composition (wt%) Fold film thickness Film composition (wt%) Fold film thickness Example Si0 ₂ Ti0 ₂ Ce0 ₂ Au ratio (nm) Si0 ₂ Ti0 ₂ Ce0 ₂ Au ratio (nra )

21 23.2 30.8 46.0 0 1.87 127 89.0 0 0 11.0 1.46 108

22 Same as above Same as above Same as above 104 Same as above Same as above Same as above Same as above 108

23 〃〃〃 83 〃〃〃〃〃 108

24 〃〃〃 104 〃〃〃〃〃 90

25 7.3 32.4 48.3 12.0 2.02 123 41.9 18.5 27.6 12.0 1.70 121

26 〃〃〃〃 123 〃〃〃〃 99

27 〃 123 〃〃〃〃〃 79

28 8.3 36.8 54.9 0 2.02 113 41.9 18.5 27.6 12.0 1.70 121

29 〃〃 113 〃〃 99

30 〃〃 113 〃〃 79

31 7.3 32.4 48.3 12.0 2.02 123 4721.1 31.4 12.0 1.70 121

32 〃〃〃〃〃 123 〃〃〃〃〃 99

33 〃〃〃〃〃 123 〃〃〃〃〃 79

34 89.0 0 0 11.0 1.46 108 23.2 30.8 46.0 0 1.87 127

35 7.3 36.8 54.9 0 2.02 82 89.0 0 0 11.0 1.46 108

36 〃〃〃〃〃 56 〃〃〃〃〃 108

37 〃〃〃〃 45 〃〃〃〃〃 108

38 〃〃〃〃 82 〃〃〃〃〃 97

39 〃〃〃〃 56 〃〃〃〃〃 97

40 〃〃〃〃〃 45 〃〃〃〃〃 97 (Table 15) Upper layer Lower layer Actual bending film composition (wt%) Fold film thickness Film composition (wt%) Fold film thickness Example i U 2 T Li 2 JU 2 Au ratio (nm) 2 1 2 CVJ 2 Au ratio (nm)

10 c

41 1 o.0 97

61.0 12.0 1.70 0 0

121 0.0 uO. 0 0 2.02 113

42 1 J 1 port '' Same as above Same as above 121 ίπΐ

| oj Same as above Same as above 92

43 121 75

44 41.9 18.5 27.6 12.0 1.70 121 7.3 32.4 48.3 12.0 2.02 123

45 99 123

46 79 123

47 41.9 18.5 27.6 12.0 1.70 99 8.3 36.8 54.9 0 2.02 113

48 79 113

49 47.5 21. 1 31.4 0 1.70 121 7.3 32.4 48.3 12.0 2.02 123

50 99 123

51 79 123

(Table 16) Example Example Lath Y a T g T uv T370 Transmission chromaticity lightness Base material (%) () (%) (%) (a / b / shi)

21 A 69.7 46.0 10.8 26.1 -5.9 / 4.4 / 83.9

22 〃 64.9 45.2 12.0 29.3 -2.6 / 3.9 / 81.2

23 〃 62.6 44.6 13.6 33.0-1.1 / -4.6 / 79.7

24 〃 65.4 45.6 12.8 31.1 2.9 / -4.2 / 81.6

25 B 34.3 30.3 2.3 6.0 8.3 / -7.0 / 60.1

26 〃 38.6 31.7 2.6 7.1 13.5 /-3.5 / 64.1

27 〃 39.9 32.4 2.7 7.3 -13.7 /-4.7 / 65.3

28 〃 48.4 38.3 2.8 7.4 -2.4 /-1.4 / 70.0

29 〃 52.3 39.9 3.1 8.2 -5.7 / 0.2 / 73.1

30 54.5 40.8 3.1 8.3 -6.3 / -0.8 / 74.7

31 〃 48.2 35.2 3.1 8.4-20.7 / 1.0 / 71.9

32 〃 47.5 35.4 3.4 9.3 -20.5 / -0.7 / 71.5

33 〃 47.0 35.8 3.3 8.9-19.0 / -2.5 / 71.1

34 A 75.0 50.0 11.7 28.4 -7.8 / 1.9 / 87.4

35 〃 57.2 42.0 31.4 12.9 0.8 /-3.4 / 75.8

36 〃 57.3 41.8 31.5 13.1 0.1 / 1.2 / 75.6

37 〃 58.6 42.6 31.3 13.2-0.8 / 2.6 / 76.5

38 〃 58.0 42.2 31.6 13.0 0.1 / -2.7 / 76.4

39 〃 58.4 42.2 31.9 13.3 -0.9 / 2.3 / 76.4

40 〃 60.2 43.2 31.1 13.1 -1.7 / 4.4 / 77.4

9 'm Ί- ΎΙ- 9' SI I '9 9

1 'ΖΙΙΙ /' ΖΖ- Ζ 1 9'S ε 98

ΈΑ ΈΑ / 5 'S / 0' G 9 '91 l9 6 '0 -2S 8

9/0 'I '91 ε · 9 6'. 0 Ό9

Ζ 9/6 'I / '61-9' Ζ \ o -g 6 • ιε 0 56 〃

1 09/9 8- / ε'9 8Ί1 L 6 'οε 6 ε

Ζ -IS / 1 '{Ί -79 · Π 0 Ό1 6 Έ 0 • οε 6 · 6Ζ

ε 'ε 9 · 8Ι ^ • L · 6ε Ζ' ^ 〃 ε

Ζ · Ζ9 / Ζ · Ζ 71 Ί Ζ Ί \ 8 '9 I · 6ε 0'

L '89 / 9 · 9 11 · 0- s · ει S 'S I · 6ε 9 V

(n / q / B) (%) (%) (%) (%) n

(S 丄 ΛΠ 丄 3 1 Ε people

(i ΐ SL € 0 / 96df / X3d ZP £ VL6 O (Table 18) Force "Las surface" Force "Las surface" Film surface Example Visible light reflectance Reflected chromaticity Visible light reflectance Reflected chromaticity

(%) (a / b) (%) (a / b)

21 7.0 4.6 / 10.8 6.7 14.6 / -19.0 22 9.5 3.0 / 5.3 13.0 0.2 / 11.8 23 11.3 0.9 / 6.4 16.1 4.1 / 12.4 24 9.7 2.8 / 6.0 13.5 -1.0 / 12.8 25 5.4 5.8 / 12.1 7.1 13.0 / -21.0 26 7.6 7.3 / 5.6 7.9 20.5 /-20.8 27 8.2 3.5 / -1.1 13.0 16. II -3.1 28 6.9 8.9 / 8.7 9.0 18.6 / -16.6 29 8.9 5.6 / -1.9 10.3 19.5 / -9.0 30 9.7 0.5 / 1.9 12.4 12.5 / 0.3 31 7.4 6.0 / -10.9 6.0 6.0 / -29.8 32 8.4 5.2 / 6.6 6.9 7.3 c 23.2 33 9.0 0.5 / -2.1 7.6 1.2 /-15.2 34 4.6 0.2 / 0.4 6.1 2.1 / 3.2 35 15.6 -0.6 / 3.9 24.5 -6.3 / 7.1 36 16.0 -0.9 / -1.3 24.4 -4.4 / -2.4 37 15.4 1.1 / -3.4 22.7 -3.4 / -5.7 38 16.2 -2.2 / 4.8 24.4 -6.2 / 6.5 39 16.7 -2.6 / -1.3 24.1 -4.0 / -3.1 40 15.6 -2.9 / -4.1 21.8 2.2 / -8.4 (Table 19) Glass surface Glass surface Film surface Film surface

Example Visible light reflectance Reflective chromaticity Visible light reflectance Reflective chromaticity

(%) (a / b) (%) (a / b)

41 6.4 9.2 / -9.4 8.0 12.7 / -12.1

42 10.0 2.3 / 7.0 12.2 8.2 / 7.9

43 11.6 2.7 / 11.0 13.7 2.0 / 14.0

44 6.1 4.0 / -7.4 6.2 -4.5 / -8.6

45 7.5 9.5 / -9.6 6.7 14.8 / -23.0

46 7.5 7.9 / 7.7 8.6 21.- 13.4

47 10.3 7.4 / -0.5 10.5 16.2 / -7.8

48 12.2 2.1 / 6.1 11.6 9. II 2.0

49 8.3 7.9 / -8.9 7.6 7.3 / -17.4

50 8.3 7.9 /-8.5 8.7 16.9 /-19.9

51 8.1 0.3 / 0.2 10.5 9.4 / -3.0

Industrial applications

INDUSTRIAL APPLICABILITY The present invention is suitable for a glass article coated with an ultraviolet absorbing colored film, particularly a glass plate coated with an ultraviolet absorbing colored film used for vehicles such as automobiles and windows of buildings.

Claims

1. Expressed as weight percent

Silicon oxide 5-5 (),

Titanium oxide 5 ~ 70,

Cerium oxide 20-80,

Gold, silver, platinum, palladium, sulfide

Force dome and cadmium selenide

Selected from the group consisting of

Tomo] 5-30 fine particles for seed coloring,

Cobalt oxide, chromium oxide, copper oxide,

Manganese oxide, nickel oxide and

Fewer selected from the group consisting of iron oxide

With one kind of coloring metal oxide 0 ~ 30,

A glass article coated with a UV-absorbing colored film comprising a glass substrate surface coated with a UV-absorbing colored film containing as a main component.

2. Between the ultraviolet absorbing and coloring film and the glass substrate or on the ultraviolet absorbing and coloring film,

Expressed in weight%,

Silicon oxide 20-1 () 0,

Titanium oxide, zirconium oxide, acid

Cerium oxide, zinc oxide and tan oxide

At least selected from the group consisting of

Also one kind of metal oxide 0 ~ 70

Gold, silver, platinum, palladium, sulfide power

From dome and selenide cadmium

At least one selected from the group consisting of

Fine particles for coloring 0 to 30

And an intermediate layer having a refractive index lower than the refractive index of the ultraviolet absorbing colored film. 2. The glass article coated with an ultraviolet absorbing colored film according to claim 1, wherein the glass article has an uppermost layer.

3. On the surface of the glass substrate, expressed as% by weight,

Silicon oxide 5-50,

Titanium oxide 5-70,

Cerium oxide 20-80,

An ultraviolet absorbing film containing, as a main component, between the ultraviolet absorbing film and the glass base material, or on the ultraviolet absorbing film, expressed in% by weight,

Gold, silver, platinum, palladium, sulfide power

From dome and selenide cadmium

At least one kind of clothing selected from the group

Fine particles for color 5-30,

Silicon oxide 5-95,

Titanium oxide, zirconium oxide, cerium oxide

From lithium, zinc oxide and tantalum oxide

At least one metal selected from the group consisting of

Oxides 0-70,

Cobalt oxide, chromium oxide, copper oxide, acid

Manganese oxide, nickel oxide and iron oxide

At least one piece of clothing selected from the group consisting of

Color metal oxides 0-30,

A UV-absorbing colored film-coated glass article having an intermediate layer or a top layer having a refractive index lower than the refractive index of the UV-absorbing film.

4. The glass substrate has a thickness of 1.5 to 5.5 mm, represented by the Lab color system, and a value of -1.0 to 1.0 and a value of 4.0 to 4. Transmitted light chromaticity with b value of 0, 10-70% ultraviolet light transmittance (at 370 nm wavelength), 40-85% visible light transmittance and 20-80% sunlight transmission The colored film-coated glass article according to any one of claims 1 to 3, wherein

5. The glass substrate is represented by the ab color system, and the transmitted light chromaticity of the value of a from 10.0 to 14.0 and the value of b from -1.0 to 4.0 is calculated. The colored film-coated glass article according to claim 4, wherein

6. The colored film-coated glass article according to claim 4, wherein said glass substrate further has an ultraviolet light transmittance (Tuv) of 5% or less.

7. Expressed in% by weight,

Silicon oxide 30 ~ 50,

Titanium oxide 5 ~ 4 5,

Cerium oxide 20-60,

However, the sum of titanium oxide and cell oxide is 35 to 55,

Fine particles for gold coloring 5 ~ 30,

, As a main component, having a refractive index of 1.65 to 1.76, a UV-absorbing colored film having a thickness of 1.5 to 5.5 mm and an ab color system, A value of a from 0 to -4.0 and-]. A chromaticity of transmitted light with a value of b from 0 to 4.0, an ultraviolet light transmittance of 10 to 70% (at a wavelength of 370 nm) A UV-absorbing colored film-coated glass article coated on the surface of a glass substrate having a visible light transmittance of 40 to 85% and a solar light transmittance of 20 to 80%.

8. The transmitted light of the glass article is represented by a point of color 0 (a = 0, b = 0), a point A ′ (a = 25, b = ()), a point B ′ (a = 0, b =-2 5), point

(a = 0, b = 2 5), and point 0 'in that order, point 0' and point A ', and point C' and point 0 ', respectively, as straight lines, point A' and point B ', and point 8. The ultraviolet absorption according to any one of claims 1 to 7, having a color tone within a sector formed by connecting B 'and point C' with an arc of a circle centered at point 0 '. Glass article coated with colored film.

9. The transmitted light of the glass article is represented by a Lab color system,

The coloring according to any one of claims 1 to 7, wherein 5.0 and b have a color tone in the range of 5.0 to 5. () and L has a transmission color represented by a lightness of 60 to 90. Coated glass articles.

10. The reflected light on the glass surface side of the glass article is calculated from the values of a and b in the Lab color system, and the value of (a ² + b ² ) ^1/2 is 10 or less. 10. The glass article coated with an ultraviolet-absorbing colored film according to any one of ranges 1 to 9.

1 1. The reflected light on the glass surface side of the glass article is calculated from the values of a and b in the Lab color system. The value of (a ² + b ² ) ¹² is 5.0 or less. The ultraviolet-absorbing colored film-coated glass article according to range 10.

12. The colored coated glass article according to any one of claims 1 to 11, wherein the glass article has a sunlight transmittance of 55% or less.

1 3. The colored coated glass article according to any one of claims 1 to 12, wherein the glass article has an ultraviolet transmittance (Tuv) of 12% or less.